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Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio

Journal Article · · Journal of CO2 Utilization
 [1];  [2];  [2];  [2];  [2];  [3];  [1];  [1]
  1. Univ. of Sao Paulo (Brazil)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Federal Univ. of Sao Carlos (Brazil)
+ Show Author Affiliations

In this study, we evaluated aspects of the CO2 hydrogenation mechanism, correlating structure-activity relationships of Cu-ZnO-ZrO2 catalysts prepared by one-pot surfactant-assisted co-precipitation with different surfactant ratios. Identifying the CO2 hydrogenation pathway intermediates is key to controlling the reaction selectivity. Experimental evidence shows that the CO2 is dissociating into CO* and O* onto the surface of the Cu-ZnO-ZrO2 catalyst. The adsorption and dissociation of CO2 were evidenced by a combination of in situ ambient-pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Fourier Transform Infrared Spectroscopy (FTIR) with a transmission cell. AP-XPS showed that the catalysts are composed of a Cu2+, Zr3+, and Zr4+ mixture and two kinds of Zn2+ species. After the H2 reduction process, only Cu2+ was reduced to Cu0. The Zn and Zr species were oxidized by the dissociated O* species. In situ transmission FTIR showed that CO was adsorbed onto the Cu+/0 sites. The catalyst with the higher surfactant molar ratio exhibited the highest CO2 conversion close to the equilibrium conversion, as well as a good methanol formation rate.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1637476
Report Number(s):
BNL--216106-2020-JAAM
Journal Information:
Journal of CO2 Utilization, Journal Name: Journal of CO2 Utilization Journal Issue: C Vol. 41; ISSN 2212-9820
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
CO2 hydrogenation
Cu-ZnO-ZrO2
Methanol
Reaction mechanism
Surfactant-assisted co-precipitation